Hydrocarbon oil composition



United States Patent Qfiflce 3,017,360 HY DROCARBON OIL COMPOSITIONHenryk A. Cyba, Chicago, Ill., assignor, by mesne asslgnments, toUniversal Oil Products Company, Chicago, 111., a corporation of DelawareNo Drawing. Filed May 23, 1958, Ser. No. 737,211 6 Claims. (Cl. 25234)This invention relates to a novel additive for hydrocarbon oil and moreparticularly to a novel method of improving hydrocarbon oil in a numberof important properties.

During processing, transportation, storage and/or use, hydrocarbon oilsgenerally deteriorate, particularly when subjected to elevatedtemperature. For example, hydrocarbon oil being subjected tofractionation or conversion is first heated to an elevated temperature.Such heating may be effected in an externally fired furnace or it may beaccomplished by heat exchange with a hotter fluid. In the first case,the hydrocarbon fluid is passed through tubes during such heating and,in many cases, deposit formation occurs in the tubes and results in lossof etficien-t heating and/or plugging of the furnace tubes. In heatexchange systems the hydrocarbon oil is passed either through tubesdisposed in a shell or through the shell surrounding the tubes. Duringheating of the oil, deposit formation occurs either within the tubes orin the hotter sections of the shell, with the result of decreasedefi'iciency in heat transfer and even in plugging of the tubes. Anotherexample in which hydrocarbon oil is passed in heat exchange is in thecase of jet fuel, Where the jet fuel is passed in heat exchange with thehot exhaust gases, both to cool the exhaust gases and to heat theincoming fuel. Temperatures as high as 500 F. or more are encounteredfor at least short periods of time,

with the result that deposit formation occurs and either' plugs the heatexchanger or interferes with efficient heat transfer.

Other examples where instability of the hydrocarbon oil is a problem arehydrocarbon oils heavier than gasoline including diesel oil, heateroil-s, burner oils, range oils, fuel oils, transformer oils, hydraulicoils, slushing oils, etc. Deposit formation in these oils isobjectionable because it results in plugging of filters, strainers,burner tips, injectors, etc., reduction in viscosity and accordingly inflowing properties, as well as the formation of varnish and sludge inthe diesel engine. In addition to preventing these objectionable depositformations, the novel additive of the present invention also functionsto retard corrosion of metal surfaces in contact with hydrocarbon oiland water. It is well known that water generally is present inhydrocarbon oils and results in corrosion of piping, pumps, shells,fr-actionators, receivers, storage tanks, etc., as well as internalequipment such as baflie plates, bubble trays, bubble caps, etc.

In addition to serving the important functions hereinbefore set forth,the novel additive of the present invention also serves to lower thepour point of the hydrocarbon oil. This is of advantage in the case ofheavier oils which are being pumped and also of particular advantage inthe case of lubricating oils, gas turbine oils, steam turbine oils, jetturbine oils, marine oils, etc. in order that the oil retain its flowingproperties at lower temperatures. In addition to reducing pour point andlowering the cold test, the additive also improves the viscosity indexof lubricating oil.

The additive of the present invention also serves an important functionin the case of gasoline or naphtha. As hereinbefore set forth, theadditive serves as a corrosion inhibitor and therefore reduces corrosionproblems during handling of the gasoline.

From the above description, it will be noted that the 3,017,360 PatentedJan. 16, 1962 novel additive to the present invention serves to improvehydrocarbon oil in a number of different ways. The hydrocarbon oilincludes gasoline, naphtha, jet fuel, kerosene, burner oil, heater oil,range oil, gas oil, fuel oil, lubricating oil, residual oil, etc. Ashereinbefore set forth, the additive may be incorporated in the oilprior to heating for further processing, or it may be incorporated inthe oil after such treatment.

In one embodiment the present invention relates to a method of improvinga hydrocarbon oil which comprises incorporating therein a stabilizingconcentration of a carboxylic acid salt of the condensation product ofan epihalohydrin compound with an amine compound having at least 12carbon atoms.

In a specific embodiment the present invention relates to a method ofpreventing deposit formation in a heat exchanger through which twofluids at different temperatures are passed which comprisesincorporating in at least one of said fluids, in an amount sufficient toprevent deposit formation, a salt of a dibasic carboxylic acidcontaining from about 6 to about 50 carbon atoms per molecule and thecondensation product of epichlorohydrin with an amine compound havingfrom about 12 to about 40 carbon atoms per molecule.

In still another embodiment the present invention relates to a method ofimproving burner oil which comprises incorporating therein a stabilizingconcentration of an oleic acid salt of the condensation product ofepichlorohydrin and tallow amine.

In still another embodiment the present invention relates to hydrocarbonoil containing a stabilizing concentration of the novel additive hereinset forth.

The novel additives of the present invention also are new compositionsof matter and are being so claimed in the present application.

As hereinbefore set forth, the novel additive of the present inventionis a carboxylic acid salt of the condensation product of anepihalohydrin compound with an amine compound having at least 12 carbonatoms. The amine compound used in preparing the reaction productcontains at least 12 carbon atoms and preferably at least 15 carbonatoms. Generally the total number of carbon atoms in the amine will notexceed about 40 carbon atoms per molecule. In a preferred embodiment theamine contains a straight chain of at least 3 carbon atoms attached tothe nitrogen atom. In this preferred embodiment, the alkyl groupattached to the nitrogen atom is of normal configuration and notsecondary, tertiary or of cyclic configuration. However, the alkyl groupmay contain branching in the chain, provided such branching occurs onthe fourth carbon atom from the nitrogen atom or further distanttherefrom.

Any suitable alkyl amine meeting the requirements set forth herein maybe used in preparing the additive of the present invention. In additionto the above requirements, it is essential that the alkyl amine is aprimary or secondary amine; that is, only one or two of the hydrogenatoms attached to the nitrogen atom are substituted by alkyl groups.Tertiary amines (no hydrogen atom attached to the nitrogen atom) cannotbe used in the present invention. It is understood that the term alkylamine is used in the present specifications and claims to includeprimary alkyl amines, secondary alkyl amines, polyamines, N-alkylpolyamines, N,N'-dialkyl polyamines, etc., all of which meet therequirements hereinbefore set forth.

Illustrative examples of primary alkyl amines include dodecyl amine,tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine,heptadecyl amine, octadecyl amine, nonadecyl amine, eicosyl amine,heneicosyl amine, docosyl amine, tricosyl amine, tetracosyl amine,

pentacosyl amine, hexacosyl amine, heptacosyl amine, octacosyl amine,nonacosyl amine, triacontyl amine, hentriacontyl amine, dotriacontylamine, tiitriacontyl amine, rtet ratriacontyl amine, pentatniacontylamine, hexatriacontyl amine, heptatriacontyl. amine, octatriacontylamine, nonatriacon-tyl amine, tetraco-ntyl amine, etc. Conveniently thelong chain amines are prepared from fatty acids or more particularlyfrom mixtures of fatty acids formed as products or by-products. Suchmixtures are available commercially, generally at lower prices and, asanother advantage of the present invention, the mixtures may be usedwithout the necessity of separating individual amines in pure state.

An example of such a mixture is hydrogenated tallow amine which isavailable under various trade names including Alamine H26D and ArmeenHTD. These products comprise mixtures predominating in alkyl aminescontaining 16 to 18 carbon atoms per alkyl group, although they containa small amount of alkyl groups having 14 carbon atoms, and also meet theother requirements hereinbefore set forth.

Illustrative examples of secondary amines include di- (dodecyl) amine,di-(tridecyl) amine, di-(tetradecyl) amine, di-(pentadecyl) amine,di-(hexadecyl) amine, di- (heptadecyl) amine, di-(octadecyl) amine,di-(nonadecyl) amine, di-(eicosyl) amine, etc. In another embodiment,which is not necessarily equivalent, the secondary amine will containone alkyl group having at least 12 carbon atoms and another alkyl grouphaving less than 12 carbon atoms, both of the alkyl groups having astraight chain of at least 3 carbon atoms attached to the nitrogen atom.Illustrative examples of such compounds include N-propyl-dodecyl amine,N-butyl-dodecyl amine, N-amyldodecyl amine, N bu-tyl-tridecyl amine,N-amyl-tridecyl amine, etc. Here again, mixtures of secondary amines areavailable commercially, usually at a lower price, and such mixtures maybe used in accordance with the present invention, provided that theamines meet the requirements hereiubefore set forth. An example of sucha mixture available commercially is Armeen 2HT which consists primarilyof dioctadecyl amine and dihexadecyl amine.

Preferred examples of N-alkyl polyamines com-prise N-alkyl1,3-diaminopropanes which the alkyl group contains at least 12 carbonatoms. Illustrative examples include N-dodecyl 1,3 diaminopropane,-N-tn'decyl-1,3- diaminoprop-ane, N tetradecyl-l,3-diaminoprop-ane, N-pentadecyl 1,3 diaminopropane, N hexadecyl-l,3-diaminopropane,N-heptadecyl 1,3 diaminopropane, N- octadecyl-1,3 diaminopropane, Nnonadecyl l,3-diammopropane, N- eicosyl-1,3-diaminopropane,N-heneicosyl-1,3 -diaminopropane, N doco-syl-1,3-diaminopropane,N-tricosyl-1,3-diaminopropane, N tetracosyl 1,3 diaminopropane, N-pentacosyl-1,3-diaminopropane, N- hexacosyl 1,3 diaminopropane, N-heptacosyl-l,3-diaminopropane, N-octacosyl 1,3 diaminopropane, N-nonacosyl 1,3 diaminopropane, N-triacontyl-1,3-diaminopropane,N-hentn'acontyl-l,3-diaminopropane, N- dotriacontyl 1,3 diaminopropane,N-tritriacontyl-1,3- diaminopropane, Ntetratriacontyl-1,3-diaminopropane, N-pentatriacontyll ,3-diaminopropane, N-hexatn'acontyl- 1,3-diaminopropane, N-heptatriacontyl1,3 diaminopropane, N-octatriacontyl-1,3-diaminopropane,N-nonatriacontyl 1,3 diaminopropane, N -tetracontyl-l,3-diaminopropane,etc. As before, mixtures are available commercially, usually at lowerprices, of suitable compounds in this class and advantageously are usedfor the purpose of the present invention. One such mixture is Duomeen Twhich is N-tallow-1,3-diaminopropane and predominates in alkyl groupscontaining 16 to 18 carbon atoms each, although the mixture contains asmall amount of alkyl. groups containing 14 carbon atoms each. Anothermixture available commercially is N-coco-l,3-diaminopropane whichcontains alkyl groups predominating in 12 to 14 carbon atoms each. Stillanother example is Nasoya 1,3 diaminopropane which predominates in alkylgroups containing 18 carbon atoms per group, although it contains asmall amount of alkyl groups having 16 carbon atoms.

While the N-alkyl-1,3-diaminopropanes are preferred compounds of thisclass, it is understood that suitable N-alkyl ethylene diamines,N-alkyl-1,3 diaminebutanes, N-alkyl 1,4 diaminobutanes,N-alkyl-1,3-diaminopentanes, N-alkyl 1,4 diaminopentanes, N-alkyl-1,5-diaminopentanes, N alkyl-1,3-diaminohexanes, N-alkyl-1,4-diaminohexanes, N alkyl-1,5-diaminohexanes,N-alkyl-l,6-diammohexanes, etc. may be employed but not necessarily withequivalent results. Also, it is understood that polyamines containing 3or more nitrogen atoms may be employed provided they meet therequirements hereinbefore set forth. Illustrative examples of suchcompounds include N-dodecyl-diethylene triamine, N tridecyl-diethylenetriamine, N tetradecyl-diethylene triamine, etc., N-dodecyl-dipropylenetriamine, N-tridecyldipropylene triamine, N-tetradecyl-dipropylenetriamine, etc., N-dodecyl-diburtylene triamine, N-tridecyl-dibutylenctriamine, N-tetradecyl-dibutylene triamine, etc., N-dodecyl-triethylenetetramine, N-tridecyl-tniethylene tetramine, Natetradecyl-triethylenetetramine, etc., N-dodecyltripropylene tetramine,N-tridecyl-tripropylene tetramine, N-tetradecyl-tripropylene tetramine,etc., N-dodecyl-tributylene tetramine, N tridecyl-tributylene tetramine,N- tetradecyl-tri-butylene tetramine, etc., N-dodecyl-tetraethylenepentamine, N-tridecyl-tetraethylene pentamine, N-tetradecyl-tetraethylene pentamine, etc., N-dodecyl-tetrapropylenepentamine, N -tridecyl -tetrapropylene pentamine,N-tetradecyl-tetrapropylene pentamine, etc., N-dodecyl-tetrabutylenepentamine, N-tridecyl-tetrabutylene pentamine,N-tetradecyl-tetrabutylene pentamine, etc.

In another embodiment, polyaminoalkanes meeting the requirementshereiubefore set forth, may be employed but generally such materials arenot available commercially and, therefore, generally are not preferred.Illustrative examples of such compounds include 1,12- diaminododecane,1,13-diaminotridecane, 1,14-diaminotetradecane, etc.

In general, it is preferred that the amine compound is a saturatedcompound and does not contain double bonds in the chain. However, insome cases, unsaturated compounds may be employed, provided they meetthe other requirements hereinbefore set forth, although not necessarilywith equivalent results. Such amine compounds may be prepared fromunsaturated fatty acids and, therefore, may be available commercially atlower cost. Illustrative examples of such amine compounds includedodecylenic amine,'didodecylenic amine, N-dodecylinic ethylene diamine,N dodecylenic 1,3 diaminopropane, oleic amine, dioleic amine, N-oleicethylene diamine, N- oleic-l,3-diaminopropane, linoleic amine,dilinoleic amine, N-linoleic ethylene diamine,N-linoleic-l,3-diaminopropane, etc. It is understood that these aminecompounds are included in the present specifications and claims byreference to amine or amine compounds.

In another embodiment of the invention, two different amines may bereacted with the epihalohydrin compound. At least one of the amines mustmeet the qualifications hereinbefore set forth. The other amine maycomprise any suitable compound containing primary and/0r secondary aminegroups. Preferred compounds comprise ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, etc., similarpropylene and polypropylene polyamines, butylene and polybutylenepolyamines, etc. In still another embodiment, other suitablenitrogen-containing compounds may be used as, for example, urea,monoethanol amine, etc.

As hereinbefore set forth, the amine compound is reacted with anepihalohydrin compound. Epichlorohydrin is preferred. Otherepichlorohydrin compounds include 1,2-epi-4-chlorobutane,2,3-epi-4-chlorobutane, 1,2-epi-5- chloropentane,2,3-epi--chloropentane, etc. In general, the chloro derivatives arepreferred, although it is understood that the corresponding bromo andiodo compounds may be employed. In some cases epidihalohydrin compoundsmay be utilized. It is understood that the different epihalohydrincompounds are not necessarily equivalent in the same or differentsubstrate and that, as hereinbefore set forth, epichlorohydrin ispreferred.

In general, 1 or 2 mols of amine compound are reacted with 1 or 2 molsof epihalohydrin compound. It is understood that, in some cases, anexcess of amine or of epihalohydrin may be supplied to the reaction zonein order to insure complete reaction, the excess being removedsubsequently in any suitable manner. When 2 mols of amine are reactedper mol of epihalohydrin compound, the amine may comprise the same ordifferent amine compound.

In a preferred embodiment of the invention, the reaction of 1 mol ofamine compound with 1 mol of epihalohydrin compound proceeds to theformation of polymeric reaction product. In this embodiment of theinvention, the reaction is first effected at a temperature Within therange hereinafter set forth, with only a portion of the reactants beingpresent in the reaction mixture. After the initial reaction iscompleted, the remaining reactants are supplied to the reaction mixtureand the reaction is completed at a higher temperature but within thesame range set forth herein. For example, a portion of the amine may befirst reacted With the epihalohydrin and then the remaining portion ofthe amine is reacted. These polymers may contain from about 3 to about20 or more recurring units and preferably from about 5 to aboutrecurring units.

The desired quantity of alkyl amine and epihalohydrin compounds may besupplied to the reaction zone and therein reacted, although generally itis preferred to supply one reactant to the reaction zone and thenintroduce the other reactant stepwise. Thus, usually it is preferred tosupply the amine to the reaction zone and to add the epihalohydrincompound step-wise, with stirring. When it is desired to react twodifferent alkyl amines With the epihalohydrin compound, theepihalohydrin compound is supplied to the reaction zone. One of theamines is added gradually, and the reaction completed, followed by theaddition of the second alkyl amine. Generally, it is preferred toutilize a solvent and, in the preferred embodiment, a solution of theamine in a solvent and a separate solution of the epihalohydrin compoundin a solvent are prepared, and these solutions then are commingled inthe manner hereinbefore set forth. Any suitable solvent may be employed,a particularly suitable solvent comprising an alcohol including ethanol,propanol, butanol, etc., 2-propanol being particularly desirable.

The reaction is effected at any suitable temperature, which generallywill be Within the range of from about 20 to about 100 C. and preferablyis within the range of from about 50 to about 75 C. A higher temperaturerange of from about 30 to about 150 C. or more, and preferably of fromabout 50 to about 100 C., is specified when the reaction is effected atsuperatmospheric pressure to increase the reaction velocity.Conveniently, this reaction is effected by heating the amine solution indilute alcohol at refluxing conditions, with stirring, gradually addingthe epihalohydrin compound thereto, and continuing the heating until thereaction is completed.

Either before or after removal of the reaction product from the reactionzone, the product is treated to remove halogen, generally in the form ofan inorganic halide salt as, for example, the hydrogen halide salt. Thismay be effected in any suitable manner and generally is accomplished byreacting the product with a strong inorganic base such as sodiumhydroxide, potassium hydroxide, etc., to form the corresponding metalhalide. The reaction to form the metal halide generally is effectedunder the same conditions as hereinbefore set forth. After this reactionis completed, the metal halide is removed in any suitable manner,including filtering, centrifugal separation, etc. It is understood thatthe reaction product also is heated sufficiently to remove alcohol andwater and this may be effected either before or after the treatment toremove the inorganic halide.

In still another embodiment, after the reaction product of an alkylamine and epihalohydrin is prepared, the reaction product may be reactedwith other nitrogen-containing compounds including, for example, alkanolamines, urea, etc., instead of with the same or different alkyl amine ashereinbefore described. Illustrative alkanol amines include ethanolamine, propanol amine, butanol amine, pentanol amine, hexanol amine,etc. As hereinbefore set forth, a oarboxylic acid salt of thecondensation product prepared in the above manner is used as an additiveto hydrocarbon oil. Any suitable carboxylic acid may be utilized informing the salt and preferably comprises a dibasic oarboxylic acidcontaining at least 6 and preferably at least l0 carbon atoms permolecule, and more particularly from about 20 to about 50 carbon atomsper molecule. The preferred acids are referred to herein as highmolecular weight polybasic carboxylic acids and include adipic, pimelic,suberic, azelaic, sebacic, phthalic, etc., aconitic, citric, etc.,hernimellitic, trimesic, prehnitic, mellophanic, pyromellitie, mellitic,etc., and higher molecular polybasic oarboxylic acids. It is understoodthat a mixture of acids may be employed.

A particularly preferred acid comprises a mixed byproduct acid beingmarketed commercially under the trade name of VR-l Acid. This acid is amixture of polybasic acids, predominantly d-ib asic, has an averagemolecular weight by basic titration of about 750, an average molecularweight of about 1000, is a liquid at 77 F., has an acid number of about150 and iodine of about 36, and contains about 37 carbon atoms permolecule.

Another particularly preferred acid comprises a mixed acid beingmarketed commercially under the trade name of Empol 1022. This dimeracid is a dilinoleic acid and is represented by the following generalformula:

This acid is a viscous liquid, having an apparent molecular Weight ofapproximately 600. It has an acid value of 180492, an iodine value of80-95, a saponificatiorr value of 185-195, a neutralization equivalentof 2903l0, a refractive index at 250C. of 1.4919, a specific gravity at15.5C./15.5C. of 0.95, a flash point of 530 F., a fire point of 600 F.,and a viscosity at C. of 100 centistokes.

As hereinbefore set forth dibasic acids containing at least 6 carbonatoms per molecule are'preferred. However, it is understood that dibasicacids containing less than 6 carbon atoms also may be employed in somecases and thus include oxalic, malonic, succinic, glutar-ic, etc.Similarly monobasic oarboxylic acids may be used in forming the salt insome cases and thus include formic, acetic, propionic, butyric, valeric,trimethylacetic, but preferablycontains at least 6 carbon atomsincluding capnoic, caprylic, lauric, myristic, palmitic, stearic,arachidic, behenic, lignoceric, cerotic, etc., decyleni'c, dodecylenic,palmito'leic, oleic, ricino leic, petroselinic, vaccenic, linoleic,linolenic, eleostearic, licanic, parinaric, gadoleic, arachidonic,cetoleic, erucic, selacholeic, etc.

It is understood that the various acids which may be used in preparingthe salt are not neccesar-ily equivalent and also that mixtures of acidsmay be employed in preparing the salts.

.Thesalt of the carboxylic acid and epihalohydrinamine condensationproduct may be prepared in any suitable manner and may comprise theacid, neutral or basic salt. When utilizing a dibasic acid in formingthe salt, the acid salt generally is preferred, although the neutralsalt may be desirable in some cases. When using a monobasic carboxylicacid in forming the salt, the neutral or basic salt in general ispreferred. The neutral salt is formed by using the reactants in aproportion to give an equivalent number of amine groups and anequivalent number of carboxylic acid groups. Thus, when using amonocarboxylic acid, one mol proportion of the carboxylic acid is usedper each amine group in the condensation product. When using adioarboxylic acid, one mol proportion of the acid per amine group in thecondensation product produces an acid salt. Therefore, when using adicarboxylic acid and a neutral salt is desired, one-half molproportionof the acid is used per each amine group in the condensation product. Insome cases an excess of acid or condensation product may be present inthe product but generally is not preferred.

The salt may be prepared in any suitable manner and, in general, isreadily prepared by mixing the acid and condensation product at ambienttemperature, preferably with vigorous stirring. While the salt isreadily prepared at room temperature, in some cases it is of advantageto heat the mixture at slightly elevated temperature which generallywill not exceed about 200 F. Excessive temperature must not be used inorder not to cause formation of esters, amides or other undesiredreaction products. Depending upon the particular condensation productand acid employed, it may be desirable to utilize a solvent, either informing a more fluid mixture of the condensation product and/ or acidbefore mixing or during the mixing thereof. Any suitable solvent may beemployed and preferably is an aromatic hydrocarbon including benzene,toluene, xylene, ethylbenzene, cumene, etc., or mixtures thereof. Inother cases the solvent may be selected from alcohols, ethers, ketones,etc. In many cases it is desired to market the salt as a solution in asuitable solvent and conveniently the same solvent is used duringmanufacture of the salt as is desired in the final product.

It is understood that the different salts which may be prepared and usedin accordance with the present invent-ion are not necessarilyequivalent. For example, one salt may be effective for a certain purposein one hydrocarbon oil, while another salt may be eifective in the samesubstrate for a different purpose or in different substrates for thesame or different purposes.

The concentration of salt to be incorporated in the hydrocarbon oil willdepend upon the particular use. For example, when utilized to preventheat exchanger deposits, the salt generally is used in a concentrationof from 1 to 1000 parts per million by weight of the hydrocarbon oil.When used for other purposes, the salt may be used in a concentration offrom about 0.0001% to about 1% or more by weight of the hydrocarbon oil.It is understood that the salt is incorporated in the hydrocarbon oil inany suitable manner and generally is effected with stirring in order toobtain intimate mixing thereof. However, when introduced in a flowingstream of oil, mixing is accomplished by turbulence normally encounteredtherein.

As hereinbefore set forth, the salt is particularly advantageous for useto prevent deposit formation in heat exchangers. Such heat exchange isutilized, for example, in a hydrotreating process in which oil issubjected to hydrogen treating in the presence of a catalyst comprisingalumina-molybdenum oxide-cobalt oxide or alumina-molybdenumsulfide-cobalt sulfide. The oil, which may comprise gasoline, kerosene,gas oil or mixtures thereof, is introduced into the process at atemperature of from about ambient to 200 F. and is passed in heatexchange with reactor efliuent products being withdrawn at a temperatureof from about 500 to about 800 F. The charge is heated by such heatexchange to a temperature of from about 300 to about 600 F., then isheated in a furnace or otherwise to a temperature of from about 625 toabout 800 F. and passed with hydrogen in contact with the catalyst. Thistreatment serves to remove impurities and to hydrogenate unsaturatescontained in the charge. Another illustration is a reforming process inwhich gasoline is contacted with hydrogen in the presence of aplatinumcontaining catalyst at a temperature of from about 700 to about1000 F. and the hot eflluent product from the reaction zone is passed incontact with the charge in order to cool the former and heat the latter.

An example in which oil is subjected to fractionation and the charge ispassed in heat exchange with the hot eflluent products is in a crudecolumn. In this column, crude oil is subjected to distillation at atemperature of from about 600 to about 700 F. in order toremove lightercomponents as overhead and/ or side streams. In some cases the chargefirst is passed in heat exchange with the overhead and/ or side streamsfrom this column and then is passed in heat exchange with the hotterproducts withdrawn from the bottom of the crude column. In this way thecharge is progressively heated and the hotter products are cooled.

The above examples are illustrative of typical uses of heat exchange toeflect economies in the process. However, difliculty is experienced inthe heat exchange due to deposit formation, with the consequentnecessity of interrupting plant operation as hereinbefore set forth. Inaccordance with the present invention, deposit formation in heatexchanger is reduced to an extent that normal plant operation need notbe interrupted for this reason.

It is understood that the advantages of the present invention may beobtained in any suitable heat exchange equipment. In general, thisequipment comprises a series of tubes or a tube coil positioned within ashell. One of the fluids is passed through the tubes, while the otherfluid is passed through the shell. The heat exchange equipment generallyis positioned externally to a fractionator or reactor. However, in somecases, the heat exchanger takes the form of a reboiler or condenser, andeither a tube coil or a shell containing tubesis positioned within thelower or upper portion of the fractionator or reactor.

When the salt of the present invention is added to a finished product,it is incorporated therein with suitable mixing, and may be used alongwith other additives to be added to the oil for specific reasons as, forexample, metal deactivator, antioxidant, synergist, cetane improver,etc. As hereinbefore set forth, the salt serves to improve the oil inmany ways including preventing deposition of sediment, preventingformation of varnish or sludge, preventing corrosion of metal surfaces,depressing pour point, preventing icing, etc. It is understood that allof these improvements are not necessarily obtained in all substrateswith the same additive. However, the different oils will be improved inone or more ways as hereinbefore set forth.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

Example I The salt of this example is the VR-l acid salt of thecondensation product of epichlorohydrin and tallow amine. Thecondensation product was prepared by the reaction of equal molproportions of hydrogenated tallow amine (Armeen HTD) andepichlorohydrin. It will be noted that the tallow amine is a mixture ofprimary amines predominating in 16 to 18 carbon atoms per alkyl group.The reaction was effected by first forming a solution of 2 mols ofepichlorohydrin in 600 cc. of a solvent mixture comprising 400 cc. ofxylene and 200 cc. of 2-propanol. A separate solution of 2 mols ofArmeen HTD was prepared in an equal volume of xylene. One mol of thelatter solution was added gradually to the epichlorohydrin solution,with stirring and heating at 5560 C. for a period of 2.5 hours. Thenanother mol of Armeen HTD was added gradually to the reaction mixture,stirred and reacted at 80 C. for 2.5 hours. One mol of sodium hydroxidethen was added with Stirring and heating at 85 90 C. for 3.5 hours,after which another mol of sodium hydroxide was added and the mixturestirred and reacted at 8590 C. for one hour. Following completion of thereaction, the mixture was cooled, filtered, and the filtrate then wasdistilled to remove the alcohol. The product was recovered as a 50% byweight solution of active ingredient in xylene.

10.04 grams of the 50% solution of the condensation product prepared inthe manner described above was mixed with 11.6 grams of VR-l acid. Ashercinbefore set forth, VR-l acid is a dibasic acid containing about 37carbon atoms per molecule. 11.6 grams of xylene was added to the mixtureso that a final solution of 0% active ingredient was prepared. Themixing was effected at room temperature with stirring, following whichthe mixture was heated at 140 F. for one hour on a water bath. Theproduct was recovered as a viscous, dark brown liquid and is an acidsalt because two equivalents of carboxylic acid groups were used pereach amine group in the condensation product.

Example II A sal-t prepared in the manner described in Example I wasevaluated as a corrosion inhibitor. In this evaluation, which is amodified MIL-1.25017 procedure, 300 cc. of depolarized isooctane, towhich 30 cc. of synthetic sea water is added, is placed in a beaker opento the atmosphere. A steel strip of 95 thickness and A" wide is weldedto a similar strip enclosed in a glass tube. The probe then is suspendedin the mixed oil-water suspension, heated to and maintained at 100 F.for 20 hours. The extent of corrosion is determined by measuring theloss in conductivity which in turn is converted to loss of steel,reported as micro inches penetration. When a blank or control sample ofthe oil-water emulsion is evaluated in the above manner, the corrosionis reported as about 150 micro inches penetration. In contrast, inanother evaluation in which 60 parts per million of the salt describedin Example I was incorporated in the oil-water suspension, the corrosionwas only 13 micro inches penetration.

From the above data it is seen that the salt of the present inventionwas very efiective in retarding corrosion.

Example III A salt prepared in the manner described in Example I alsowas evaluated as a corrosion inhibitor by a different method. Thismethod is known as the Humidity Cabinet Test. In this test, a highlypolished steel panel is dipped into a viscous naphthenic mineral oil,excess oil is drained, and the panel is placed in a humidity cabinetmaintained at 120 F. in an atmosphere saturated with water. The panelsare rotated slowly, and the days required for visible corrosion toappear on the panel is reported. A panel dipped in a control sample ofthe oil (not containing this additive) undergoes visible corrosion in2-3 hours.

1% by weight of a salt prepared in the manner described in Example I wasincorporated in another sample of the oil. The panel dipped in this oiland then placed in the humidity cabinet did not undergo visiblecorrosion until after 768 hours of exposure at 120 F. to the atmospheresaturated with water. Thus, it will be seen that this additive served toconsiderably reduce corrosion.

Example IV The salt of this example is the oleic acid salt of thecondensation product of epichlorohydrin and tallow amine. Thiscondensation was effected in substantially the same manner as describedin Example I. The salt was prepared by mixing 100.2 grams of the 50% byweight solution of the condensation product in xylene with 41 grams ofoleic acid and 41 grams of xylene. The mixture was stirred and heated at124 F. for 30 minutes. The product was a neutral salt, was recovered asa 50% solution of active ingredient, and was a slightly viscous, reddishbrown liquid.

Example V The salt prepared in the manner described in Example IV isused as a pour point depressant in lubricating oil. The lubricating oilis a commercial S.A.E. 20 Mid-Continent solvent extracted oil which,without additive, has an ASTM cold test of 5 F. and an ASTM pour pointof 10 F. 1% by weight of the salt prepared as described in Example IIIis incorporated in a sample of this lubricatnig oil and serves to reducethe ASTM cold test and the ASTM pour point.

Example VI A salt prepared in substantially the same manner as describedin Example I is evaluated in a method referred to as the Erdco Test. Inthis method, heated oil is passed through a filter, and the timerequired to develop a difierential pressure across the filter of 25 in.Hg is determined. It is apparent that the longer the time, the moreefiective is the additive. However, with a very eifective additive, thetime to reach a difierential pressure across the filter of 25 in. Hg islengthened beyond reasonable limits that the test is stopped after about300 minutes and the differential pressure at that time is reported.

The oil used in this example is a commercial J.P.-6 jet fuel. Whenevaluated for use as a jet fuel, which normally encounters highertemperature, the test is run at a higher temperature. The preheater isrun at a temperature of 400 F. and the filter is run at a temperature of500 F. The jet fuel, without additive, developed a differential pressureacross the filter of 25 in. Hg in 60 minutes. The salt prepared in themanner described in Example I is added in a concentration of 0.005% byweight to another sample of the jet fuel and serves to considerablylengthen the time before a diiferential pressure of 25 in. Hg isreached.

Example VII A salt prepared in substantially the same manner asdescribed in Example I is also evaluated according to the C.F.R. fuelcoker thermal stability test. In this test, the oil heated to thespecified temperature is passed through'the annular space surrounding aheated inside tube of 17" length and /2" diameter positioned within anoutside tube of W inside diameter. The inside tube is heated by means ofa heating coil positioned therein to a temperature of either 300 or 400F. depending upon the particular fuel being evaluated. The test isconducted for 300 minutes, at a pressure of pounds per square inch, anda flow rate of 6 pounds of fuel per hour. Following the run theequipment is dismantled, 13" or less of the inner tube is marked off inl increments and the deposits on the outside surface of the heated innertube are rated by visual comparison with standard metal coupons. Ingeneral the rating is substantially as follows:

clean and bright metal dulled but not discolored light yellowdiscoloration yellow to tan discoloration anything darker or heavierthan 3 The ratings for the individual 1" increments are added togetherto give a final tube rating. Military specifications for jet fuelsrequire that none of the 1" increments rates poorer than 3.

The fuel evaluated in this example is a J.P.6 commercial fuel and wastested at 400 F. A sample of the jet fuel evaluated in the above mannerhad a tube rating of 15. 50 parts per million by weight of the saltdescribed above is incorporated in another sample of this fuel and, whenevaluated in the above manner, willconsiderably lower the tube rating.

Example VIII The salt prepared in the manner described in Example I isused in a commercial Unifining Unit to prevent heat exchanger deposits.In this unit gasoline is subjected to hydrotreating in the presence ofan alumina-molybdenum oxide-cobalt oxide or alumina-molybdenumsulfide-cobalt sulfide catalyst. The gasoline charge is introduced at atemperature of 200 F. and is passed in heat exchange with reactoreflluent being withdrawn at a temperature of about 675 F. This serves toheat the charge to a temperature of about 550 F. and to cool the reactoreffluent to a temperature of about 325 F. In this unit the charge ispassed through the tubes of the exchanger and the reactor efliuent ispassed through the shell. 25 parts per million by weight of the salt isincorporated in the gasoline before the same is passed into theexchanger and this serves to prevent heat exchanger deposits and topermit extended use of the heat exchanger without requiring shuttingdown the plant because of the plugging of the heat exchanger tubes.

I claim as my invention:

1. Hydrocarbon oil containing from about 0.000l% to about 1% by weightof a salt of a car-boxylic acid of from about 6 to about 50 carbon atomsper molecule and the condensation products of from 1 to 2 mols of anepihalohydrin compound with from 1 to 2 mols of an aliphatic amine offrom about 12 to about 40 carbon atoms per molecule, said salt being thereaction product of from 1 to 2 mol proportions of acid per 1 to 2 molproportions of amine group in the condensation product.

2. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof a salt of a polybasic carboxylic acid containing from about 6 toabout 50 carbon atoms per molecule and the condensation product of from1 to 2 mols of epichlorohydrin with from 1 to 2 mols of an alkyl aminehaving from about 12 to about 40 carbon atoms per molecule, said saltbeing the reaction product of from 1 to 2 mol proportions of acid per 1to 2 mol proportions of amine group in the condensation product.

3. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof a salt of a dibasic carboxylic acid containing from about 6 to about50 carbon atoms 12 per molecule and the condensation product of from 1to 2 mols of epichlorohydrin with from 1 to 2 mols of an alkyl aminehaving about 12 to about 40 carbon atoms per molecule, said salt beingthe reaction product of from 1 to 2 mol proportions of acid per 1 to 2mol proportions of amine group in the condensation product.

4. Hydrocarbon oil containing from about 0.000l% to about 1% by weightof an acid salt of a dibasic carboxylic acid containing from about 20 toabout carbon atoms per molecule and the condensation product of from 1to 2 mols of epichlorohydrin with from 1 to 2 mols of tallow amine, saidsalt being the reaction product of from 1 to 2 mol proportions of acidper 1 to 2 mol proportions of amine group in the condensation product.

5. Hydrocarbon oil containing from about 0.000l% to about 1% by weightof a salt of a monobasic carboxylic acid containing from about 6 toabout 50 carbon atoms per molecule and the condensation product of from1 to 2 mols of epichlorohydrin with from 1 to 2 mols of an alkyl aminehaving from about 1 2 to about 40 carbon atoms per molecule, said saltbeing the reaction product of from 1 to 2 mol proportions of acid per 1to 2 mol proportions of amine group in the condensation product.

6. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an oleic acid salt of the condensation product of from 1 to 2 mols ofepichlorohydrin with from 1 to 2 mols of tallows amine, said salt beingthe reaction product of from 1 to 2 mol proportions of acid per 1 to 2mol proportions of amine group in the condensation product.

References Cited in the file of this patent UNITED STATES PATENTS1,954,133 Jacobs Apr. 10, 1934 2,130,947 Carothers Sept. 20, 19382,143,388 Schlack Jan. 10, 1939 2,214,352 Schoeller et a1. Sept. 10,1940 2,454,547 Bock et a1. Nov. 23, 1948 2,475,410 Smith et a1. July 5,1949 2,479,480 Dudley Aug. 16, 1949 2,587,546 Matuszak Feb. 26, 19522,753,372 Lundberg July 3, 1956 2,908,640 Dougherty Oct. 13, 1959

1. HYDROCARBON OIL CONTAINING FROM ABOUT 0.0001% TO ABOUT 1% BY WEIGHTOF A SALT OF A CARBOXYLIC ACID OF FROM ABOUT 6 TO ABOUT 50 CARBON ATOMSPER MOLECULE AND THE CONDENSATIO PRODUCTS OF FROM 1 TO 2 MOLS OF ANEPIHALOHYDRIN COMPOUND WITH FROM 1 TO 2 MOLS OF AN ALIPHATIC AMINE OFFROM ABOUT 12 TO ABOUT 40 CARBON ATOMS PER MOLECULE, SAID SALT BEING THEREACTION PRODUCT OF FROM 1 TO 2 MOL PROPORTIONS OF ACID PER 1 TO 2 MOLPROPORTIONS OF AMINE GROUP IN THE CONDENSATION PRODUCT.